Photographic element

ABSTRACT

GROUPS IN 50, 50 - X and X molar percent proportions, respectively, X being not more than 50 and R being an alkyl group having from 1 to 4 carbon atoms. The photographic element has reduced propensity to curling and to becoming sticky after stabilization processing.   A photographic element for use in silver halide photography having a silver halide emulsion layer, a protective layer, a subbing layer or a diffusion-transfer image-receiving layer, each using gelatin as the main binding component, in which into one of said layers are incorporated a nonionic water-soluble polymer and a phase separation inhibitor containing the

United States Patent 1 Tsuji et al.

[ 1 Apr. 15, 1975 [30] Foreign Application Priority Data Jan. 19,1971Japan 46-13211 [52] US. Cl 96/87 R; 96/85; 96/67;

96/114; 96/ll4.4; 96/114.5; 96/114.7; 117/161 R; 117/161 UC; 117/161 C[51] Int. Cl G03c H78 [58] Field of Search 96/85, 67, 114, 114.4,96/114.5, 114.7, 87 R; 117/16] R, 161 UC, 161 C [56] References CitedUNITED STATES PATENTS 2,964,403 12/1960 Beekman et al. 96/85 2,980,5344/1961 Printy et al. 96/85 3,085,897 4/1963 Priest et al.... 96/1143,161,519 12/1964 Alsup 96/85 3,165,412 1/1965 Minsk et al. 96/1143,369,901 2/1968 Fogg et al. 96/85 3,397,988 8/1968 Van Paesschen....96/85 3,425,857 2/1969 Bacon et a1 96/85 Grabhofer et al. 96/1 14 Yanoet al. 96/1 14 Primary Examiner-Norman G. Torchin AssistantExaminer-Edward C. Kimlin Attorney, Agent, or FirmSughrue, Rothwell,Mion, Zinn & Macpeak [57] ABSTRACT A photographic element for use insilver halide photography having a silver halide emulsion layer, aprotective layer, a subbing layer or a diffusion-transferimage-receiving layer, each using gelatin as the main binding component,in which into one of said layers are incorporated a nonionicwater-soluble polymer and a phase separation inhibitor containing the-CH2-CH- ,-CH-CH- 0COCH COOH COOH and - CH CH COOH COOR groups in 50, 50X and X molar percent proportions, respectively, X being not more than50 and R being an alkyl group having from 1 to 4 carbon atoms.

The photographic element has reduced propensity to curling and tobecoming sticky after stabilization processing.

21 Claims, No Drawings PHOTOGRAPHIC ELEMENT CROSS-REFERENCE TO RELATEDAPPLICATIONS The present application is a divisional application of 5our earlier co-pending application Ser. No. 219,179 filed on Jan. 19,1972, and claims priority from Jan. 19, 1971 based on Japanese PatentApplication No. 1321/71.

BACKGROUND OF THE INVENTION 1. Field of the invention 7 This inventionrelates to photographic elements, and more particularly to compositionof layers to be provided 'on a photographic element support.

2. Description of the Prior Art Photographic elements in generalcomprise a support material such as paper, a synthetic resin film, aglass or metallic plate, with a subbing layer optionally being providedthereon for the purpose of enhancing the adhesivity between the supportand photographic layer adjacent thereto, together with a silver halideemulsion layer, usually with a protective layer provided thereon toprevent damage to said emulsion layer, the latter two layers beingapplied onto the surface of the foregoing support or subbing layer.Furthermore, as one special kind of photographic material there is animagereceiving element used in the diffusion transfer photographicprocess, which element comprises an imagereceiving layer havingincorporated therein a catalytic substance, i.e., silver deposits orso-called development nuclei, in a dispersed form for reduction of asoluble silver complex transported by diffusion from a photographiclight-sensitive element.

' As the binding agent for these photographic elements, gelatin hasheretofore been used in almost all cases due to its outstandingphotographic and physical properties. Since gelatin is a naturalsubstance, however, its use has suffered from the disadvantage that theproperties of gelatin largely depend upon the raw materials andmanufacturing processes used to form it; and often it is therefore notpossible to insure constant quality in the finished product. Besidessuch a disadvantage, the use of gelatin presents some other problems.For instance, it is sensitive to changes in temperature and humidity andtends to curl. Furthermore, in the stabilization process wherein aphotographic element is processed in a stabilizing solution containingammonium thiocyanate, the surface of a gelatin film which constitutes aphotographic layer becomes sticky after stabilization.

Recently, in an attempt to eliminate these defects, various kinds ofsynthetic polymers have been pro- Unit No.

posed as substitutes for gelatin as a binding agent for photographiclayers. These include, for example, polyvinyl alcohol, polyacrylamide,polyvinyl pyrrolidone, poly-1-vinyl-2-methylimidazole, sodiumpolyacrylate, an acrylamide-1-vinyl-2-methylimidazole copolymer and anacrylamide-l-vinyl-2-methylimidazole-acrylic acid copolymer. Thesesynthetic polymers, however, are not superior gelatin in various otherphotographic and physical properties, so that in practice gelatin isused.

It has been attempted to employ gelatin with such synthetic polymers,thereby maintaining the superior properties of the gelatin andcompensating for the defects of the same by means of the properties ofthe synthetic polymers. However, when a portion of the gelatin isreplaced by a nonionic water-soluble polymer, complete mixing of bothcomponents is optional proportions cannot be effected andphase-separation takes place.

To attempt to overcome this effect, a method has been proposed wherein athird substance is added to prevent the phase separation. For example,in Japanese Patent Publication No. 4,272/64 there is described the useof a methyl vinyl ether maleic anhydride copolymer (hereinafter referredto as MVE/MA) or an amide or ester thereof as a phase-separationinhibitor upon using gelatin with polyvinyl alcohol.

SUMMARY OF THE INVENTION We have found that the compounds disclosedhereinafter are extremely effective as phase-separation inhibitors uponadmixing gelatin with nonionic polymers. Furthermore, we have alsoconfirmed the following advantages: the coating composition preparedusing such compounds can be applied onto a support more uniformly thanin the case of using the prior art phaseseparation inhibitor, i.e., theabove-described copolymer (MVE/MA) or an amide or ester thereof; thephotographic elements produced have little tendency to curl, and theyshow little tendency to be sticky after stabilization, if such is used.

Thus, the present invention provides a photographic element comprising asupport having thereon at least one layer comprising gelatin, a nonionicwater-soluble polymer and a polymer, said polymer comprising 50 molepercent of vinyl acetate, (50 x) mole of maleic acid and mole of halfalkyl ester of maleic acid, wherein x is 0 2; 50 and the alkyl group has1 to 4 carbon atoms.

The polymer of the present invention, which can be employed as aninhibitor for phase-separation between gelatin and the nonionicwater-soluble polymer, may be characterized by the following chemicalunits and the specified proportion thereof.

Atomic groups Proportion contained (50 X) molar COOH COOH Unit No.Atomic groups Proportion contained '3 CH (IIH- Xmo1ar% COOH COOR (Xbeing not more (R being an alkyl than 50) group having from 1 1:0 4carbon atoms.)

The nonionic water-soluble polymers which may be S E; y" 2' 047 used inaccordance with the present invention include 5 polyvinyl alcohols,polymers Of acrylamlde 01' its derlv- (R n butyl) (R means alkyl groupof the half ester of atives such as acrylamide, N-methylacrylamide, N-

()See Page relmeso ethylacrylamide, N, N-dimethylacrylamide, N, N- WUnit I 50 niolar 7! diethylacrylamide, N-methoxymethylacrylamide, 8"}: gmolar?! 0.52 N-ethoxymethylacrylamide, N-morpholinoacrylamide, 20 mo orN-morpholinomethylacrylamide, the corresponding polymers ofmethyacrylamide or its derivatives, polyvinyl methyl ethers, polyvinylpyrrolidones, polyvinyl oxazolidones, polyvinyl caprolactams, solublestarch and cellulosic derivatives such as hydroxyethyl cellulose ormethyl cellulose. Besides these homopolymers, there may also be usedwater-soluble copolymers consisting of the monomer units mentionedabove.

Among the nonionic water-soluble polymer polyvinyl alcohol is the mosttypical one. Any known polymer which is used together with gelatin inthe photographic art may be employed.

The phase-separation inhibitors used according to the present inventionmay be obtained by synthesizing a l l (polymerization ratio) copolymerof vinyl acetate and maleic anhydride by means of any conventionalradical polymerization method, and heat-treating the copolymer in wateror an alcohol having from l to 4 carbon atoms to effect hydrolysis oralcoholysis of the same. The decomposition reaction may also be par- 40tially carried out to produce the half ester. By the procedure, the

- CH CH i l COOH COOH group which initially occupies molar percent ofthe copolymer is converted into the CH CH 50 coon COOR group by X molarpercent. In the present invention, the above-described decompositionreaction can be eliminated, so that the range of X is 0 g X 50. Theproperties of the polymer are substantially not affected on theproportion of X.

Several examples of such phase-separation inhibitors will be given belowwhere the values of the intrinsic viscosity are taken in a methanolicsolution of each phaseseparation inhibitor at 300C.

Intrinsic viscosity l Unit I 50 molar 0.64

Unit 2 50 molar "/1 ll Unit 1 50 molar 7: 0.73

Unit 3 50 molar '71 (R ethyl) According to the present invention,gelatin and the nonionic water-soluble polymer can be used in admixturewith the phase-separation inhibiting polymer in photographic layers.These photographic layers include not only a light-insensitive layersuch as a protective or uppermost layer, a subbing or under-coatedlayer, an image receiving layer for diffusion-transfer process, whichlayer may also contain nuclei for precipitating silver, such ascolloidal silver or heavy metal sulfides, but also a light-sensitivelayer such as a light-sensitive silver halide emulsion layer. Thephase-separation inhibiting polymer of the present invention may beadded to a mixture to be coated at any stage before coating. The polymermay also be added to a silver halide emulsion during preparationthereof.

The proportions of gelatin, nonionic water-soluble polymer andphase-separation inhibiting polymer may be varied depending upon thespecific requirement of the photographic layers being produced and thespecific compound to be used. ln general, the preferred proportions areset out below.

gelatin about 5 about by weight nonionic water-soluble about about 1571by weight polymer phase-separation about 5 about [5'71 by weightinhibitor The phase-separation inhibitors used according to the presentinvention may be of any molecular weight, although it is most preferredto use those having an intrinsic viscosity [1 as measured in amethanolic solution at 30C., of about 0.05 to about 5.0, preferablyabout 0.3 to about 2.0.

Suitable support material include any of those used in photography suchas cellulose acetate, synthetic resins such as polyesters, polystyrenesor polycarbonates, paper, or resin coated paper such as polyethylenecoated paper.

The copolymers used according to the present invention remarkedlyimprove the compatibility between gelatin and nonionic water-solublepolymers, and are extremely effective for the prevention ofphaseseparation which often takes place.

The present invention can be applied to varied silver halide emulsionsusing silver chloride, silver bromide, silver chlorobromide, silveriodobromide and/or silver chloroiodobromide, and mixtures thereof.

The emulsions to which the present invention may be applied may bechemically sensitized by any conventional method, for example usinglabile-sulfur containing compounds such as ammonium thiosulfate orethylthiourea (see, for example, P. Glafkindes, Chimie Photographique; 2eme Edition Photocinema, Paul Montel, Paris, 1957, pages 297299); goldcompounds such as complexes of monovalent gold and thiocyanic acid (seelbid., page 301) or any combination of these compounds. The emulsionsmay be optically sensitized by incorporating thereinto spectralsensitizers such as cyanine or merocyanine dyes (see, for example,Shinichi Kikuchi, et a], Kagaku-Shashin Binran, Maruzen Co., Ltd.. 1959,pages -24). Furthermore, they may be stabilized by any stabilizers wellknown in the art, for example, heterocyclic compounds such asbenzotriazole, l-phenyl-5-mercaptotetrazole, 4-hydroxy-6- methyl-1,3,3a,7-tetrazaindene or 6-thioctic acid, mercury compounds such asmercumallylic acid (see Japanese Patent Publication No. 22, 063/64), orbenzenesulfonic acid. In addition, the emulsions may be hardened usinghardening agents such as formaldehyde, mucochloric acid, chromium alumor triazine derivatives (see, for example, Belgian Pat. No. 641,044), ora combination of these hardeners with hardening adjuvants such asresorcin or resorcin aldehyde. Into the emulsions there may beincorporated surface active agents such as saponin, sodium alkylbenzenesulfonate or an addition polymer of an alkylphenol and sultone (seeBritish Pat. No. 1,024,808) in order to facilitate the application ofsaid emulsions. Furthermore, the emulsions may be sensitized usingpolyalkylene oxide derivatives such as condensation products of analkylphenol and polyethylene oxide.

The emulsions prepared in accordance with the present invention can beused, after the addition of couplers, in the manufacture of naturalcolor photographic films or papers. Furthermore, by increasing the ratioof the water-soluble polymer to gelatin, the developed film can beremoved by means of rinsing, so that it may be used as a negative layerfor use in the so-called multi-layer diffusion transfer process (C.E.Neblette, Photography, its Materials and Processes, 6th Edition, D. VanNostrand Co., Princeton, New Jersey, 1962, pages 371-373) The presentinvention will now be further illustrated by the followingnon-limitative examples.

EXAMPLE 1 A silver halide photographic emulsion thickness (4 microns)was prepared which contained g. silver chloride and 10 g. gelatin, andwas divided into three equal portions A, B and C. lnto each portionthere was Composition of the developer:

Metol 1 Anhydrous sodium sulfite 15 Hydroquinone 4 Sodium carbonatemonohydrate 27 Potassium bromide 1 Water to make 1,000 c.c. Compositionof the fixing solution:

C rystalline sodium thiosulfate 240 g.

Anhydrous sodium sulfite 15 g Glacial acetic acid 13.3 g Borax 7.5 g.Potash alum powder 15 g.

Water to make 1.000 c.c.

After drying each specimen under the conditions mentioned above, thecurling value was determined by measuring across the center of thecircular form the distance (.r em) between the tips which were closestupon the curling, and the value (10 x) cm was taken as the curlingvalue. The results of the measurement are shown in Table 1.

Table 1 Specimens Condition 1 Condition 2 A 5.2 cm. 9.8 cm. B(Separation took place in the emulsion phase and uniform application wasimpossible.) C 0.4 cm. 1.2 cm.

As is evident from Table 1, the photographic paper using the compoundsaccording to the invention (Specimen A) showed extremely low curlingvalues as compared with the photographic paper using gelatin alone(Specimen A). No changes were found in the photographic propertiesbetween Specimens A and C.

EXAMPLE 2 A silver halide-gelatin emulsion (thickness: 4 microns) waspreparedwhich contained 20 g. silver chloride and 10 g. gelatin, and,after addition of 10 g. hydroquinone as a developing agent, was dividedinto two equal portions A and B, into which were added the followingsolutions, respectively:

Emulsion A 200 c.c. ofa 10 weight percent aqueous solution of gelatin.

Emulsion B 180 c.c. of a 10 weight percent aqueous solution of polyvinylalcohol plus 20 c.c. of a 10 weight percent aqueous solution of aphaseseparation inhibitor (1).

Emulsions A and B were each thoroughly agitated and applied onto aphotographic base paper of g./m.'- to give photographic papers A and B,respectively, for use in a stabilization process. These photographicpapers were each developed in an activator having the composition shownbelow, after which they were processed in a stabilizing solutioncontaining Composition of the activator:

Anhydrous sodium sulfite Sodium hydroxide Potassium bromide Water tomake 1,000 c.c.

EXAMPLE 3 A silver chlorobromide emulsion was prepared which contained30 molar percent of silver bromide and 60 g. of gelatin and, afteraddition of 10 g. of hydroquinone as a developing agent, applied onto aphotographic baryta-coated paper of 135 g./m On top of the coating layerthere was further applied a thin protective layer of the followingcomposition, thereby giving a photographic paper for use in thestabilization process.

Formulation of the protective layer composition:

Gelatin 5 g. P.V.A. l5 g.

Phase-separation inhibitor (ll) 1.5 g.

Water to make L000 c.c.

EXAMPLE 4 Colloidal nickel sulfide nuclei were incorporated into anaqueous solution having the composition as shown below and applied ontoa photographic base paper of 85 g./m On top of the coating layer therewas further applied a stripping layer mainly containing sodium alginateto give an image-receiving paper for use in the silver salt diffusiontransfer process. The image-receiving paper was dipped for severalseconds in a developer (composition is shown below) for use in thesilver salt diffusion transfer process while held in tight surfacecontact with a negative paper having a silver halide emulsion layer foruse in the diffusion transfer process, which negative paper had beenexposed to light. The image-receiving paper, after being separated fromthe negative paper after seconds showed an extremely low curlingtendency and was satisfactory.

Amount of nickel sulfide in the layer was 0.6 mg/m Amount of sodiumalginate in the layer was 0.2 g/m".

20g. 30 g. 4 g.

Composition of the developer for use in the silver salt diffusiontransfer process:

Anhydrous sodium thiosulfate Potassium sulfite potassium bromideHydroquinonc Phenidone Sodium hydroxide Water to make 1.000 c.c.

EXAMPLE 5 A silver halide-gelatin emulsion was prepared which contained20 g. AgCl and 10 g. gelatin; and was divided into four equal portions,into which the following compounds were added, respectively:

Sample Substances added 200 c.c. of a 1071 aqueous solution of gelatin Amixture of I c.c. of a l0 /r aqueous solution of hydroxycthyl celluloseand 20 c.c. of a 10% aqueous solution of phaseseparation inhibitor (ll)(Substances according to the invention). A mixture of 180 c.c. of a l0/1aqueous solution of acrylamide and 20 c.c. of a l0/( aqueous solution ofphase-separation inhibitor (lll). (Substances according to theinvention) A mixture of Hi0 cc. of a 10% aqueous solution of P.\'.A. and20 c.c. of a l0'7r aqueous solution of phase-separation inhibitor (lV)(Substances according to the invention).

Emulsions A to D were each thoroughly agitated and.

then applied onto a photographic baryta-coated paper of 95 g./m to givecorresponding photographic papers. These photographic papers weresubjected to the same processing as in Example 1 and examined for theircurling properties to find that the samples B to D using the substancesof the invention showed little curling tendency and were satisfactory ascompared with sample A using gelatin alone.

The invention has been described in detail with particular reference topreferred embodiments thereof but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention as described hereinabove and as defined in the appendedclaims.

What we claim is:

1. A light-sensitive photographic element comprising a support havingthereon at least one silver halide emulsion layer which consistsessentially of silver halide, gelatin, a nonionic water-soluble polymerwhich is photographically compatible with said gelatin and a polymerwhich is a phase-separation inhibitor for said gelatin and said nonionicwater-soluble polymer, said polymer comprising 50 mole percent of vinylacetate (50 X) mole percent of maleic acid and X mole percent of a halfalkyl ester of maleic acid, wherein X is 0 X 50 and the alkyl group insaid half alkyl ester has 1 to 4 carbon atoms, wherein the proportion ofsaid gelatin, said nonionic water-soluble polymer and said polymer isabout 5 to about 70 percent by weight, about to about 15 percent byweight and about 5 to about 15 percent by weight, respectively.

2. A light-sensitive photographic element comprising a support havingthereon at least two layers, at least one of said layers being a silverhalide emulsion layer and at least one of said layers containinggelatin, a nonionic water-soluble polymer which is photographicallycompatible with said gelatin and a polymer which is a phase-separationinhibitor for said gelatin and said nonionic water-soluble polymer, saidpolymer comprising 50 mole percent of vinyl acetate, (50 X) mole percentof maleic acid and X mole percent of a half alkyl ester of maleic acid,wherein X is 2 X 50 and said alkyl group in said half alkyl ester has 1to 4 carbon atoms, wherein the proportion of said gelatin, said nonionicwater-soluble polymer and said polymer is about 5 to about 70 percent byweight, about 90 to about percent by weight and about 5 to about 15percent by weight, respectively, said at least one of said layers whichcontains gelatin, a nonionic water-soluble polymer and a polymerconsisting essentially of said components, with the proviso that whensaid components are in a silver halide emulsion layer silver halide isfurther present.

3. A light-sensitive photographic element as claimed in claim 1 wherein50 mole percent, (50 X) mole percent and X mole percent total 100 molepercent.

4. A light-sensitive photographic element as claimed in claim 1 whereinsaid nonionic water-soluble polymer is selected from the groupconsisting of polyvinyl alcohol; polymers of an acrylamide ormethacrylamide, polyvinyl methyl ether, polyvinyl pyrrolidone, polyvinyloxazolidone, polyvinyl caprolactams, soluble starch and cellulosederivatives.

5. A light-sensitive photographic element as claimed in claim 1 whereinX is 50 and said phase-separation inhibitor has an intrinsic viscosity.measured in a methanolic solution at 30C, of 0.64.

6. A light-sensitive photographic element as claimed in claim 1 whereinsaid phase-separation inhibitor contains said vinyl acetate and saidhalf alkyl ester of maleic acid in which the alkyl group of said halfalkyl ester is an ethyl group, in 50 molar percent proportions,respectively, said phase-separation inhibitor having an intrinsicviscosity, measured in a methanolic solution at 30C, of 0.73.

7. A light-sensitive photographic element as claimed in claim 1 whereinsaid phase-separation inhibitor contains said vinyl acetate, said maleicacid and said half alkyl ester of maleic acid, the alkyl group of saidhalf alkyl ester being an n-butyl group, in 50, 30 and molar percentproportions, respectively, said inhibitor having an intrinsic viscosity,measured in a methanolic solution at 30C, of 0.2.

8. A light-sensitive photographic element as claimed in claim 1 whereinsaid phase-separation inhibitor contains said vinyl acetate, said maleicacid and said half alkyl ester of maleic acid, the alkyl group of saidhalf alkyl ester being a methyl group, in 50, 20 and 30 molar percentproportions, respectively, said phaseseparation inhibitor having anintrinsic viscosity, measured in a methanolic solution at 30C, of 0.52.

9. A light-sensitive photographic element as claimed in claim 1 whereinsaid phase-separation inhibitor has an intrinsic viscosity measured in amethanolic solution at 30C in the range of from 0.3 to 2.0.

10. A light-sensitive photographic element as claimed in claim 1 whereinsaid polymer contains said 7 half alkyl ester of maleic acid.

11. A light-sensitive photographic element as claimed in claim 2 whereinsaid nonionic water-soluble polymer is selected from the groupconsisting of polyvinyl alcohol; polymers of an acrylamide ormethacrylamide, polyvinyl methyl ether, polyvinyl pyrrolidone, polyvinyloxazolidone, polyvinyl caprolactams, soluble starch and cellulosederivatives.

12. A light-sensitive photgraphic element as claimed in claim 2 whereinX is 50 and said phase-separation inhibitor has an intrinsic viscosity,measured in a methanolic solution at 30C, of 0.64.

13. A light-sensitive photographic element as claimed in claim 2 whereinsaid phase-separation inhibitor contains said vinyl acetate and saidhalf alkyl ester of maleic acid, in which the alkyl group of said halfalkyl ester is an ethyl group, in 50 molar percent proportions,respectively, said phase-separation inhibitor having an intrinsicviscosity, measured in a methanolic solution at 30C, of 0.73.

14. A light-sensitive photographic element as claimed in claim 2 whereinsaid phase-separation inhibitor contains said vinyl acetate, said maleicacid and said half alkyl ester of maleic acid, the alkyl group of saidhalf alkyl ester being an n-butyl group, in 50, 30 and 20 molar percentproportions, respectively, said inhibitor having an intrinsic viscosity,measured in a methanolic solution at 30C, 0.2.

15. A light-sensitive photographic element as claimed in claim 2 whereinsaid phase-separation inhibitor contains said vinyl acetate, said maleicacid and said half alkyl ester of maleic acid, the alkyl group of saidhalf alkyl ester being a methyl group, in 50, 20 and 30 molar percentproportions, respectively, said phaseseparation inhibitor having anintrinsic viscosity, measured in a methanolic solution at 30C, of 0.52.

16. A light-sensitive photographic element as claimed in claim 2 whereinsaid phase-separation inhibitor has an intrinsic viscosity measured in amethanolic solution at 30C in the range of from 0.3 to 2.0.

17. A light sensitive photographic element as claimed in claim 2 whereinsaid polymer contains said half alkyl ester of maleic acid.

18. A light-sensitive photographic element as claimed in claim 2 wherein50 mole percent, 50 X mole percent and X mole percent total 100 molepercent.

19. A light-sensitive photographic element as claimed in claim 2 whereinsaid at least one layer is a protective layer.

20. A light-sensitive photographic element as claimed in claim 2 whereinsaid at least one layer is a subbing layer.

21. A light-sensitive photographic element as claimed in claim 2 whereinat least one layer is an image-receiving layer for a diffusion transferprocess.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT N0. 3, 877,947

DATED 1 April 15, 1975 INVENTOR(S) I Nobuo TSUJI et: a1

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

IN THE HEA DING:

Foreign Application Priority Data De1ete-- 46-1321l-- insert 1321/71Signed and sealed this 10th day of June 1975.

(SEAL) Attest:

C. MARSHALL DANNV Commissioner of Patents and Trademarks RUTH C. MASONAttesting Officer

1. A LIGHT-SENSITIVE PHOTOGRAPHIC ELEMENT COMPRISING A SUPPORT HAVINGTHEREON AT LEAST ONE SILVER HALIDE EMULSION LAYER WHICH CONSISTSESSENTIALLY OF SILVER HALIDE, GELATIN, A NONIONIC WATER-SOLUBLE POLYMERWHICH IS PHOTOGRAPHICALLY COMPATIBLE WITH SAID GELATIN AND A POLYMERWHICH IS A PHASESEPARATION INHIBITOR FOR SAID GELATIN AND SAID NONIONICWATERSOLUBLE POLYMER, SAID POLYMER COMPRISING 50 MOLE PERCENT OF VINYLACETATE (50 - X) MOLE PERCENT OF MALEIC ACID AND X MOLE PERCENT OF AHALF ALKYL ESTER OF MALEIC ACID, WHEREIN X IS 0 X 50 AND THE ALKYL GROUPIN SAID HALF ALKYL ESTER HAS 1 TO 4 CARBON ATOMS, WHEREIN THE PROPORTIONOF SAID GELATIN, SAID NONIONIC WATER-SOLUBLE POLYMER AND SAID POLYMER ISABOUT 5 TO ABOUT 70 PERCENT BY WEIGHT, ABOUT 90 TO ABOUT 15 PERCENT BYWEIGHT AND ABOUT 5 TO ABOUT 15 PERCENT BY WEIGHT, RESPECTIVELY.
 2. Alight-sensitive photographic element comprising a support having thereonat least two layers, at least one of said layers being a silver halideemulsion layer and at least one of said layers containing gelatin, anonionic water-soluble polymer which is photographically compatible withsaid gelatin and a polymer which is a phase-separation inhibitor forsaid gelatin and said nonionic water-soluble polymer, said polymercomprising 50 mole percent of vinyl acetate, (50 - X) mole percent ofmaleic acid and X mole percent of a half alkyl ester of maleic acid,wherein X is 0 < or = X < or = 50 and said alkyl group in said halfalkyl ester has 1 to 4 carbon atoms, wherein the proportion of saidgelatin, said nonionic water-soluble polymer and said polymer is about 5to about 70 percent by weight, about 90 to about 15 percent by weightand about 5 to about 15 percent by weight, respectively, said at leastone of said layers which contains gelatin, a nonionic water-solublepolymer and a polymer consisting essentially of said components, withthe proviso that when said components are in a silver halide emulsionlayer silver halide is further present.
 3. A light-sensitivephotographic element as claimed in claim 1 wherein 50 mole percent,(50 - X) mole percent and X mole percent total 100 mole percent.
 4. Alight-sensitive photographic element as claimed in claim 1 wherein saidnonionic water-soluble polymer is selected from the group consisting ofpolyvinyl alcohol; polymers of an acrylamide or methacrylamide,polyvinyl methyl ether, polyvinyl pyrrolidone, polyvinyl oxazolidone,polyvinyl caprolactams, soluble starch and cellulose derivatives.
 5. Alight-sensitive photographic element as claimed in claim 1 wherein X is50 and said phase-separation inhibitor has an intrinsic viscosity,measured in a methanolic solution at 30*C, of 0.64.
 6. A light-sensitivephotographic element as claimed in claim 1 wherein said phase-separationinhibitor contains said vinyl acetate and said half alkyl ester ofmaleic acid in which the alkyl group of said half alkyl ester is anethyl group, in 50 molar percent proportions, respectively, saidphase-separation inhibitor having an intrinsic viscosity, measured in amethanolic solution at 30*C, of 0.73.
 7. A light-sensitive photographicelement as claimed in claim 1 wherein said phase-separation inhibitorcontains said vinyl acetate, said maleic acid and said half alkyl esterof maleic acid, the alkyl group of said half alkyl ester being ann-butyl group, in 50, 30 and 20 molar percent proportions, respectively,said inhibitor having an intrinsic viscosity, measured in a methanolicsolution at 30*C, of 0.2.
 8. A light-sensitive photographic element asclaimed in claim 1 wherein said phase-separation inhibitor contains saidvinyl acetate, said maleic acid and said half alkyl ester of maleicacid, the alkyl group of said half alkyl ester being a methyl group, in50, 20 and 30 molar percent proportions, respectively, saidphase-separation inhibitor having an intrinsic viscosity, measured in amethanolic solution at 30*C, of 0.52.
 9. A light-sensitive photographicelement as claimed in claim 1 wherein said phase-separation inhibitorhas an intrinsic viscoSity measured in a methanolic solution at 30*C inthe range of from 0.3 to 2.0.
 10. A light-sensitive photographic elementas claimed in claim 1 wherein said polymer contains said half alkylester of maleic acid.
 11. A light-sensitive photographic element asclaimed in claim 2 wherein said nonionic water-soluble polymer isselected from the group consisting of polyvinyl alcohol; polymers of anacrylamide or methacrylamide, polyvinyl methyl ether, polyvinylpyrrolidone, polyvinyl oxazolidone, polyvinyl caprolactams, solublestarch and cellulose derivatives.
 12. A light-sensitive photgraphicelement as claimed in claim 2 wherein X is 50 and said phase-separationinhibitor has an intrinsic viscosity, measured in a methanolic solutionat 30*C, of 0.64.
 13. A light-sensitive photographic element as claimedin claim 2 wherein said phase-separation inhibitor contains said vinylacetate and said half alkyl ester of maleic acid, in which the alkylgroup of said half alkyl ester is an ethyl group, in 50 molar percentproportions, respectively, said phase-separation inhibitor having anintrinsic viscosity, measured in a methanolic solution at 30*C, of 0.73.14. A light-sensitive photographic element as claimed in claim 2 whereinsaid phase-separation inhibitor contains said vinyl acetate, said maleicacid and said half alkyl ester of maleic acid, the alkyl group of saidhalf alkyl ester being an n-butyl group, in 50, 30 and 20 molar percentproportions, respectively, said inhibitor having an intrinsic viscosity,measured in a methanolic solution at 30*C, 0.2.
 15. A light-sensitivephotographic element as claimed in claim 2 wherein said phase-separationinhibitor contains said vinyl acetate, said maleic acid and said halfalkyl ester of maleic acid, the alkyl group of said half alkyl esterbeing a methyl group, in 50, 20 and 30 molar percent proportions,respectively, said phase-separation inhibitor having an intrinsicviscosity, measured in a methanolic solution at 30*C, of 0.52.
 16. Alight-sensitive photographic element as claimed in claim 2 wherein saidphase-separation inhibitor has an intrinsic viscosity measured in amethanolic solution at 30*C in the range of from 0.3 to 2.0.
 17. A lightsensitive photographic element as claimed in claim 2 wherein saidpolymer contains said half alkyl ester of maleic acid.
 18. Alight-sensitive photographic element as claimed in claim 2 wherein 50mole percent, 50 - X mole percent and X mole percent total 100 molepercent.
 19. A light-sensitive photographic element as claimed in claim2 wherein said at least one layer is a protective layer.
 20. Alight-sensitive photographic element as claimed in claim 2 wherein saidat least one layer is a subbing layer.
 21. A light-sensitivephotographic element as claimed in claim 2 wherein at least one layer isan image-receiving layer for a diffusion transfer process.